Copolymers of acetylenic acrylates and methacrylates

ABSTRACT

THE COPOLYMERS DISCLOSED HEREIN ARE OF ACETYLENIC ACRYLATES AND METHACRYLATES HAVING THE FORMULA CH2=C(R)COO-Z-C$CH WHEREIN R REPRESENTS HYDROGEN OR METHYL AND Z REPRESENTS A DIVALENT HYDROCARBON RADICAL OF AT LEAST 2 CARBON ATOMS. POLYMERIZATION OF THE ACETYLENIC ACRYLATES AND METHACRYLATES IN FREE RADICAL POLYMERIZATIONS GENERALLY RESULT IN CROSSLINKED OR GELLED PRODUCTS SINCE THE FREE RADICALS WILL ACTIVATE POLYMERIZATION THROUGH THE ACETYLENIC AS WELL AS THROUGH THE ACRYLIC UNSATURATION. THEREFORE THE COPOLYMERS ARE ADVANTAGEOUSLY PREPARED BY ANIONIC POLYMERIZATION. THE COMONOMERS ARE THOSE WHICH ARE COPOLYMERIZABLE WITH ACRYLATES AND METHACRYLATES IN ANIONIC POLYMERIZATIONS. TYPICAL COMONOMERS ARE STYRENE, ITS HOMOLOGS AND DERIVATIVES, MONOUNSATURATED ACRYLATES AND METHACRYLATES, ACRYLONITRILE, VINYL ESTERS, VINYL CHLORIDE, VINYLIDENE CHLORIDE, MONOALPHAOLEFINS, ETC. THE COPOLYMERS ARE PARTICULARLY VALUABLE FOR POST-TREATMENT AND POSTREACTIONS, SUCH AS BROMINATION, DECABORONATION, THERMAL AND RADICAL CROSSLINKING, MANNICH REACTION WITH AN ALDEHYDE AND AMMONIA OR A MONO- OR DI-SUBSTITUTED AMINE, OR REACTION WITH NITRILE OXIDES, ALDEHYDES, KETONES, EPOXIDES, SODAMIDE, ETC. THE COPOLYMERS CAN BE TAILORED TO GIVE ULTIMATE PROPERTIES ACCORDING TO THE TYPE AND THE PROPORTION OF COMONOMERS AND THE PROPORTION OF ACETYLENIC GROUPS AS WELL AS THE TYPE OF POSTREACTANT OR POST-TREATMENT.

United States Patent 3,562,218 COPOLYMERS 0F ACETYLENIC ACRYLATES ANDMETHACRYLATES Gaetano F. DAlelio, South Bend, lnd., assignor to GeigyChemical Corporation, Ardsley, N.Y., a corporation of New York NoDrawing. Filed June 28, 1968, Ser. No. 740,973 Int. Cl. C08f /18 US. Cl.260-67 13 Claims ABSTRACT OF THE DISCLOSURE The copolymers disclosedherein are of acetylenic acrylates and methacrylates having the formulaCH =C(R)COO-ZCECH wherein R represents hydrogen or methyl and Zrepresents a divalent hydrocarbon radical of at least 2 carbon atoms.Polymerization of the acetylenic acrylates and methacrylates in freeradical polymerizations generally result in crosslinked or gelledproducts since the free radicals will activate polymerization throughthe acetylenic as well as through the acrylic unsaturation. Thereforethe copolymers are advantageously prepared by anionic polymerization.The comonomers are those which are copolymerizable with acrylates andmethacrylates in anionic polymerizations. Ty'pioal comonomers arestyrene, its homologs and derivatives, monounsaturated acrylates andmethacrylates, acrylonitrile, vinyl esters, vinyl chloride, vinylidenechloride, monoalphaolefins, etc. The copolymers are particularlyvaluable for post-treatment and postreactions, such as bromination,decaboronation, thermal and radical crosslinking, Mannich reaction withan aldehyde and ammonia or a monoor di-substituted amine or reactionswith nitrile oxides, aldehydes, ketones, epoxides, sodamide, etc. Thecopolymers can be tailored to give ultimate properties according to thetype and the proportion of comonomers and the proportion of acetylenicgroups as well as the type of postreactant or post-treatment.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to copolymers of acetylenic acrylates and methacrylates withcomonomers. More specifically, it relates to copolymers with comonomerscapable of copolymerization with the acetylenic acrylates in anionicallyactivated polymerizations.

Related prior art Some monomeric acetylenic acrylates and methacrylatesand their homopolymers are disclosed in a doctorate thesis submitted in1965 by Robert C. Evers to the Graduate School of the University ofNotre Dame. However, the homopolymers of these are found to have certaindisadvantages and are more difiicult to control in postreactions becauseof the high degree of unsaturation in the unpolymerized acetylenicradicals.

However, no polymers are shown of acetylenic acrylates or methacrylateshaving four carbons or more in the acetylenic group and having aterminal acetylene (C::CH) group. Propargyl acrylate and methacrylatehomopolymers are shown but these are more inclined to crosslink and haveother disadvantages as shown hereinafter. Moreover, copolymers ofl-acryloxy-Z-butyne (Z-butyne-l-yl acrylate) and l-methacryloxy-Z-butyne(Z-butyne-yl methacrylate) are shown but these do not have terminalacetylene groups.

STATEMENT OF THE INVENTION In accordance with the present invention, ithas now been found that the disadvantages of having high concen-3,562,218 Patented Feb. 9, 1971 trations of unusaturated acetylenicgroups present during postreaction or ultimate other treatments or usesof the homopolymers are avoided by forming copolymers of acetylenicacrylates and methacrylates of the formula CH C(R)COOZCECH, wherein R ishydrogen or methyl and Z is a divalent hydrocarbon radical of at least 2carbon atoms, with a comonomer copolymerizable with the acetylenicacrylate or methacrylate under anionic activation. The copolymer can betailored for ultimate properties according to the type and proportion ofcomonomer, the proportion of acetylenic acrylate or methacrylate and thetype of postreactant or treatment effected on the acetylenic groups.Advantageously there is at least 15% by weight of the comonomer present,preferably 50% or more of the comonomer, and at least 1%, preferably atleast 5% of the acetylenic acrylate or methacrylate present in thecopolymer molecules.

Therefore, where it is desirable to impart certain prop erties topolymers of various polymerizable monomers such as the acrylates,methacrylates, styrenes, acrylonitrile, vinyl esters, vinyl chloride,vinylidene chloride, monoalpha-olefins, e.g. propylene, butene-l,isobutylene, pentene-l, etc., this is possible by copolymerizing withsuch monomers at least 1%, preferably at least 5% of the above-describedacetylenic acrylate to produce the copolymers of this invention whichare readily susceptible to post-treatments and postreaetions forproduction of the desired properties in the copolymers.

The Z group can be any divalent hydrocarbon group having at least twocarbon atoms and preferably one having no more than 10 canbon atoms. Itis found that acetylenic groups of four or more carbon atoms givepolymer products of improved properties as compared to the correspondingpropargyl acrylate polymers, such as greater solubility in lower costsolvents, improved water-resistance, :and better ductility andflexibility. Typical groups include ethyelne, phenylmethylene,methylmethylene (ethylidene), ethylmethylene, cyclohexylmethylene,cycloheptylmethyiene, tolylmethylene, benzylmethylene, phenylethylene,trimethylene, pentamethylene, octarnethylene, decamethylene,dodecamethylene, phenylene, tolylene, naphthylene, cyclohexylene,cycloheptylene, etc.

While the Z groups listed above do not contain ethylenic unsaturation,such groups containing ethylenic unsaturation can be used, althoughthere is no particular advantage in their use, provided that theunsaturation does not cause premature crosslinking during thepreparation of linear polymers.

Typical acetylenic esters that canbe used are the following acrylatesand methacrylates:

3-butyne-2-yl, 3-butyne-1-yl, l-phenyl-3-butyne-1-yl,1-cyclohexyl-3-butyne-1-yl, 1-benzyl-3-butyne-l-yl,1-phenethyl-3-butyne-1-yl, l-cycloheptyl-3-butyne-l-yl,1-propyl-3-butyne-1-yl, l-amyl-3-butyne-l-yl, 1-hexyl-3-butyne-1-yl,2-phenyl-3 -butyne-l-yl, 4-pentyne-1-yl, 4-pentyne-2-yl, 4-pentyne-3-yl,1-phenyl-4-pentyne-1-yl, 1-cyclohexyl-4-pentyne-1-yl,1-benzyl-4-pentyne-1-yl, l-phenethyl-4-pentyne-2-yl,1-propyl-4-pentyne-3 -yl,

5 -hexyne-1-yl,

5 -heXyne-2-yl,

3 7-octyne-2-yl, 9-decyne-l-yl, p-ethynylphenyl, 4-ethynyl-1-naphthyl,4-ethynyl-l-cyclohexyl, p-ethynylbenzyl, 4-ethynylcyclohexylmethyl, etc.

Typical comonomers that can be used in forming the copolymers includethe following monounsaturated acrylates and methacrylates: methyl,ethyl, propyl, butyl, amyl, octyl, decyl, phenyl, tolyl, xylyl,ethylphenyl, naphthyl, diphenyl (phenylphenyl), benzyl, phenethyl,methylcycloheptyl, etc.; styrene and its various homologs andderivatives such as vinyl naphthalene, methylvinylnaphthalene, vinyltoluene, vinyl xylene, vinyl ethylbenzene, a-methylstyrene, vinyldiphenyl, methylvinyldiphenyl, etc.; vinyl esters, such as vinylacetate, vinyl benzoate, methylvinylphthalate, vinyl butyrate, etc.;vinyl chloride, vinylidene chloride, acrylonitrile, etc.

In attempting to polymerize or copolymerize the acetylenic acrylates andmethacrylates used in the practice of this invention, the use of freeradical-generating activators, such as peroxy compounds, azo compounds,etc. generally result in a substantial degree of polymerization in theacetylenic unsaturation as well as in the ethylenic unsaturation withresultant crosslinking and a high degree of gellation. While a smallamount of gellation is permissible, in which case the gell can beseparated and the remaining ungelled polymer can be used, it isundesirable to have a high proportion of gelled polymer since it isdifficult to post-treat or postreact a polymer in this form.

Therefore, the copolymers of this invention are advantageously preparedby anionic activators which produce little or no polymerization in theacetylenic unsaturation. Where there is a small amount of suchpolymerization, resulting in such a small amount of gell formation thatit can be tolerated, the ungelled portion of the polymer is recoveredand then processed as described hereinafter. In such cases, the gelledportion can be brominated and used as non-inflammable filler in resinsand other compositions.

Methods disclosed in the literature for conducting both random and blockcopolymerizations are suitable for the purpose of this invention.Suitable anionic polymerizations are described in DAlelio U.S. Pats.Nos. 3,203,915, particularly columns 14-16, and 3,309,423, running fromline 51 in column 3 through line 55 of column 7. Typical anionicactivators are also disclosed therein.

For example the anionic polymerization can be initiated by alkali metalhydrides such as NaH, LiH, KH, CsH, including various complexes thereof,such as the metal alkyls of Li, Na, K and Cs with the hydrocarbon groupbeing methyl, ethyl, propyl, isopropyl, butyl, amyl, isoamyl, benzyl,triphenylmethyl, phenyl, naphthyl, octyl, etc., preferably containing nomore than 12 carbon atoms in a hydrocarbon group.

Also suitable are Grignard reagents having the formula RMgX, where R" isa hydrocarbon group as listed above and X is halogen. Typical examplesof these are phenyl magnesium bromide, butyl magnesium bromide andchloride, vinyl magnesium bromide, allyl magnesium bromide, etc.

The free alkali metals such as lithium, sodium and potassium can also beused as initiators, including combinations of alkali metals and aromaticcompounds such as naphthalene, anthracene, a-methyl styrene tetramer,styrene, etc. and liquid ammonia solutions of the alkali metals. Alsouseful are ketyls which are the reaction products of alkali or alkalineearth metals with ketones, such as benzophenone in ether, for examplethe sodium reaction product of benzophenone, etc.

Solvents or diluents may be used, if desired, and these can be selectedfrom the class of aliphatic and aromatic hydrocarbons, ketones, ethers,and esters, such as butane, propane, hexane, cycloheptane, octane,benzene, toluene, xylene, dimethyl ether, diethyl ether, dibutyl ether,tetrahydrofurane, dioxane, diphenyl ether, dibenzyl ether, dimethylethyleneglycol ether, dibutyl ethylene glycol ether, diethyl diethyleneglycol ether, etc.

The anionic polymerization can be carried out at temperatures rangingfrom C. to about 80 C. Although the range of 40 C. to 60 C. isadvantageous, it is generally more practical to operate in the range of-20 C. to 40 C.

The anionic polymerizations produced linear polymers having a pluralityof repeating units of the formula The linear polymer chain also hasother repeating units therein which are derived from the comonomers,such as the monounsaturated acrylates and methacrylates and styrene,which have repeating units Which can be represented as follows:

wherein R is a hydrocarbon radical, preferably of 1-8 carbon atoms.

One of the chief advantages of the copolymers of this invention is thatit allows broad and versatile modification of polymer properties. Thus,when a high proportion of the comonomer is used, the properties resemblethose of the homopolymers of such comonomers and by having copolymerizedtherewith an acetylenic acrylate or methacrylate as in this invention,it is possible to postreact or post-treat the resultant copolymers so asto permit modifications in a manner desired from the properties that thepolymer of the comonomer by itself would possess. For example,polymethylmethacrylate has little flame resistance. By producing acopolymer of methyl methacrylate with acetylenic acrylate ormethacrylate monomer as taught in the present application, it ispossible to postbrominate the copolymer and thereby produce a polymerresembling polymethmethacrylate in a number of respects in accordancewith the proportion of methylmethacrylate repeating units therein andsimultaneously imparting flame resistance to the copolymer in accordancewith the porportion of brominated acetylenic acrylate or methacrylaterepeating units therein. Flame resistance can likewise be imparted toacetylenic copolymers of the acrylates, methacrylates styrene, and othercomonomers indicated above.

In addition, various other postreactions and posttreatments can beconducted on the copolymers of this invention, such as: decarboronationby reaction with decaborane; crosslinking by the application of heat orthe generation of free radicals, with or without other monomers present;the Mannich reaction with an aldehyde and ammonia or a monoordi-substituted amine; reaction with nitrile oxides; reaction withaldehydes in the presence of a base such as NaOH, etc., producingprimary alcohols when processed with formaldehyde and secondary alcoholswhen using ther aldehydes; reactions with ketones in the presence of analkali metal base to produce tertiary alcohols; reaction with ethyleneoxide or other epoxide including diepoxides; conversion to metallicderivatives by dissolving or suspending the polymer in ammonia andadding sodamide or forming it in situ by the addition of sodium metal tothe ammonia, or by the addition of butyl lithium to the ammonia; and theformation of copper, zinc, cobalt or other salts by adding salts of suchmetals to a dioxane solution of the sodium or lithium salt of thepolymer.

The various reactions are illustrated schematically as follows:

(1) Postbromination:

(2) Decaboronation:

- 2 tu iz CH2 COOZCECH COOZCH=CHB H (Formula C) O OZCH-CH lU IO (FormulaD) (3) Crosslinking (without another comonomer) CH C (R) C o o z C=CHooozp=on -CH2(B(R) (Formula E) (3a) Crosslinking (with styrene ascomonomer):

-CHzO(R)- o o z o=orr (Formula F) (4) Mannich reaction:

CH2C(R) 011 0 RgNH CH2C (R) COOZCECH COOZCECCH2NR'2 (Formula G) (R ishydrogen or hydrocarbon such as R.")

(5) Nitrile oxide reaction:

CH2C(R)+ R"CNO -CH2C(R)- COOZCECH COOZ(J.:(|}H

o CR

(Formula H) (5a) Dinitrile oxide reaction (crosslinking):

(6) Aldehyde and ketone reaction:

COOZ CECC(RI)2OH (Formula K) COOZCECH (6a) Bromination of acetylenicalcohol from 6:.LBr

(Formula N) From the above reactions, it will be noted that thecopolymers of this invention are capable of numerous postreactions andpost-treatments and that numerous modifications in the properties of thecopolymers can be effected.

Since the copolymers can be either random copolymers, wherein theacetylenic repeating units are distributed throughout the length of thelinear copolymer, or block copolymers with the acetylenic repeatingunits either in the middle or at the ends of the linear chain of thecopolymer, or in various spaced segments in the linear chain of thecopolymer the modified properties effected by the postreaction orpost-treatment can be positioned whenever desired in the copolymermolecules. Procedures for preparing block copolymers are disclosed inthe aforementioned Pat. No. 3,309,423 and on page 827 of the Journal ofPolymer Science, vol. 5 (1967 The bromination and decaboronationreactions are efiected using conditions similar to those for theaddition of the corresponding reagents to more simple acetyleniccompounds.

The Mannich reaction for the replacement of the hydrogen on a terminalacetylenic group with an aminomethyl radical likewise uses theconditions suitable for corresponding reactions for more simpleacetylenic compounds. As defined above, the R can represent hydrogen, orthe various aliphatic, cycloaliphatic or aromatic hydrocarbon groupsindicated above. The resulting products can be used as rust inhibitors,interfacial agents, antifoam agents, acid absorbers, etc.

The reaction with nitrile oxides (RCNO) produces an oxazoline ring asshown in the reaction above. This postreaction raises the softeningpoint of the copolymer by at least C. When a dinitrile oxide is used,crosslinking can be effected, also as shown in the reactions above.

By reaction of the acetylenic repeating unit with aldehydes or ketones,alcohol groups can be introduced. With formaldehyde, the resultingalcohol group is a primary alcohol group, with other aldehydes theresulting groups are secondary alcohol groups, and with ketones theproducts have tertiary alcohol groups. When sufiicient alcohol groupsare added, the polymers are made soluble enough to be dissolved inalcohol and in some cases in water. Consequently, this reaction can beused to produce thickening agents.

The alcohols produced as described above still have an acetylenicradical in the same repeating units and therefore the polymer may bepostbrominated. The alcohol group can also be reacted with ethyleneoxide or other epoxide and such addition continued until the product isdefinitely soluble in water. This reaction when catalyzed by a tertiaryamine can be effected at room temperature. The use of diepoxides caneffect crosslinking of the polymer molecules.

The acetylenic polymers can be converted to various metallic derivativesby dissolving or suspending the polymer in liquid ammonia and thenadding NaNH or forming the same in situ by adding metallic sodium to theliquid ammonia. The resulting sodium acetylide derivative can be used invarious reactions, such as substitution of alkyl or other groups byreaction with an alkyl halide, or other metals such as copper, zinc,cobalt, etc. can be substituted for the sodium by adding thecorresponding salt to a dioxane solution of the sodium salt of thepolymer. Lithium salts can also be made by reaction of the polymer withbutyllithium and the corresponding subsequent reactions can be performedas in the case with the sodium salt.

In these various postreactions, there are generally some of the originalacetylenic repeating units remaining unreacted in the ultimate copolymerso that the ultimate copolymer has a variety of repeating unitsincluding that derived from the comonomer, such as styrene,methylmethacrylate, etc., also from unreacted acetylenic repeatingunits, and the repeating units resulting from the postreaction asindicated above in the various reactions.

The practice of this invention is best illustrated by the followingexamples. These examples are given merely by Way of illustration and arenot intended to limit the scope of the invention in any way nor themanner in which the invention can be practiced. Unless specificallyindicated otherwise, parts and percentages are given as parts andpercentages by weight.

EXAMPLE I General procedure for anionic copolymerization A -necked glassflask is used as the reaction vessel. This is connected with anevacuation means for producing a high-vacuum and fitted with anexternally driven magnetic stirrer, one of the side arms of the flaskbeing attached to a 50-ml. round-bottomed flask and also fitted with astopcock crowned with a serum cap, and a helium inlet tube. A solutionof about 50% total monomer mixture in tetrahydrofurane is stored overcalcium hydride in the round-bottom flask for at least 8 hours and thendegassed twice at 3 10- mm. Hg. The reaction vessel is flamed in astream of helium and then the monomer and the solvent are distilled intothe reaction vessel. The system is then pressured with helium toslightly above atmos pheric pressure and the reaction vessel then cooledto the desired temperature. In most cases, unless otherwise specified,this temperature is 40 C. Then initiator solution, in most cases sodiumnaphthalene solution is injected volumetrically by means of a hypodermicsyringe through the serum cap. The initiator to monomer mole ratio isusually about 1:40. The copolymerization is allowed to proceed withcontinued agitation until no further increase in viscosity is observed.The initiator is then destroyed by injection of 3 parts of methanol intothe solution mixture. The resultant copolymers are isolated byprecipation in a non-solvent, redissolved and if high purity productsare desired reprecipitated 3 times in a suitable solvent-nonsolventsystem. The polymer solutions are filtered through sintered discs beforereprecipitation. For purification of acrylonitrile copolymers,dimethylformide is used as the solvent and methanol as the precipitant.With other copolymers, benzene is used as the solvent and heptane as theprecipitant. About 0.2% 2,G-di-tert-butyl-p-cresol is used as inhibitorin both solvent and precipitant. The isolated copolymers are dried toconstant weight in a vacuum at about C. The filtrate is evaporated underreduced pressure to isolate hexane-soluble polymers if present. Theinfrared spectra of the monomers and polymers are recorded and theintrinsic viscosities of representative samples of linear polymers aredetermined.

EXAMPLE Ia Anionic block copolymerization Block copolymerization isadvantageous in that this permits better control of the number ofacetylenic structures and the positioning thereof than is the case withrandom copolymers.

For anionic block copolymerization, the monomers are added andpolymerized individually. Thus, the procedure of Example I is repeatedexcept that only one monomer is used in the initial polymerization andthen, instead of destroying the initiator, a second monomer is added andthe polymerization is continued possibly with the addition of moreinitiator. In this way a block copolymer is formed in which the firstmonomer, such as styrene or methyl methacrylate, forms the center coreof the linear polymer chain and the second monomer, such as anacetylenic monomer, forms the terminal portions of the linear polymericchain. If desired this procedure can be repeated one or more times togive a number of blocks of the respective monomer repeating unitsthrough the linear chain. Eventually, when suflicient blocks have beenadded, the initiator is destroyed and the resultant copolymer processedas in Example I.

EXAMPLE II Post-bromination Into a glass-stoppered flask there is placeda solution of 0.6 part of copolymer prepared according to Example I anddissolved in 3 parts of carbon tetrachloride. To this is added twice thetheoretical amount of bromine calculated for complete addition to thheacetylenic groups in the copolymer. The resulting mixture is wellagitated to assure thorough mixing and then the flask is stoppered,cooled to 020 C. and allowed to stand until the bromine ceases to react.At 0 C., it is generally allowed to stand for a week; at 5 C., for a fewhours; and at 20 C., a few minutes is generally suflicient. At the endof this time, 15 parts of heptane is added and the precipitated polymeris isolated by filtration and then redissolved and reprecipitated twice,carbon tetrachloride being used as the solvent and heptane as theprecipitant. The resulting copolymer has repeating units represented byFormulas A and B as given above. When the amount of bromine is notgreatly in excess of 1 mole per acetylenic group therein, there are morerepeating units of Formula A and when a considerable excess over 1 moleof bromine is used there are also repeating units of Formula B and when2 moles or more of bromine are used, there are more repeating unitsofFormula B than Formula A. In each case however, there are also repeatingunits that Were present in the starting copolymer. Similar results areobtained using block copolymers prepared as in Example Ia.

EXAMPLE III Thermal crosslinking In this procedure, a 10% solution of acopolymer made according to the procedure of Example I is prepared indry benzene. Samples of the copolymer solution are poured onto glassplates and the solvent allowed to evaporate at room temperature. Thenthe glass plates with the copolymer layers thereon are placed in an ovenat C. for 8 hours. The resultant films are insoluble in chloroform,carbon disulfide, acetone and dimethylformamide. The crosslinked polymerhas crosslinkages as shown above by Formula E. Similar results areobtained with block copolymers of Example Ia.

EXAMPLE IV Free-radical crosslinking A 10% solution of a copolymer madeaccording to Example I is prepared in benzene. To this solution there isadded 0.25% benzoyl peroxide based on the weight of copolymer. Afterthorough mixing, samples of the resultant copolymer solution are pouredon glass plates and the solvent allowed to evaporate. The plates withthe layers thereon are placed in an oven at 100 C. for one hour. Filmsare thereby formed which are insoluble in benzene, acetone, chloroformand dimethylformamide. The crosslinked polymer has crosslinkages asshown above by Formula E. Similar results are obtained when blockcopolymers of Example Ia are used.

EXAMPLE V Postreaction with decaborane Into a round-bottomed 3-neckedflask fitted with a reflux condenser, a mechanical stirrer and anitrogen inlet, there are added about 0.013 mole of a copolymer preparedas in Example I and 5 parts of decaborane, the amount of decaboranebeing in excess of the stoichiometric amount. To this mixture there isadded 1.8 parts of acetonitrile dissolved in 175 parts of dry toluenetogether with 0.1 part of ditertiary-butyl-p-cresol as inhibitor. Thisreaction mixture is refluxed for 84 hours at which time the resultingsolution is poured into 350 parts of vigorously stirred heptane. Theprecipitated polymer is isolated by filtration and washed well withheptane to remove any unreacted decaborane. The product is insoluble incarbon tetrachloride, chloroform, and carbon disulfide but is soluble intoluene and acetone. A toluene solution of the polymer is poured intoheptane and the precipitated polymers isolated and then dried in avacuum at room temperature. The pale yellow product is heated on aFisher-Johns melting point apparatus and the softening point isrecorded. This is repeated with similar success with a block copolymerprepared as in Example Ia.

EXAMPLE VI Mannich reaction (a) Into a round-bottom, 3-necked flaskfitted with a mechanical stirrer, a reflux condenser, and a thermometerare placed 0.2 mole of a copolymer prepared according to Example I, 24parts of diethylamine, parts of paraformaldehyde and 75 parts ofdioxane. The reaction mixture is heated on a steam bath with vigorousstirring for 8-24 hours and then subjected to vacuum distillation torecover the product. Analysis shows that the acetylenic groups are stillpresent and that there are also diethylaminomethyl groups present. Thismaterial is found to be suitable as a rust-inhibitor, an interfacialagent, an antifoaming agent and an acid absorber.

(b) Similar results and corresponding products are obtained when theabove procedure is repeated using in place of the diethylamine,equivalent amounts of dipropylamine, monopropylamine, dihexylamine,diphenylamine, dicyclohexylamine, dibenzylamine, ditolylamine,monophenylamine, dimethylamine and ammonia except that when ammonia andthe volatile amines are used, pressure equipment is used to prevent lossof the ammonia or amine by excessive pressure. Actually, it is foundadvantageous in such cases to conduct the reaction for a short while ata lower temperature and then gradually raise the temperature to thatobtained on a steam bath. In each case satisfactory results areobtained. Similar results are obtained with block copolymers of ExampleIa.

EXAMPLE VII Postreaction with nitrile oxide (a) The procedure of ExampleVI is repeated using in place of the amine and the paraformaldehyde ofthat example 0.33 mole of phenylnitrile oxide. In each case thepostreacted resin product has a softening point of at least 100 C. abovethat of the starting copolymer.

(b) Similar results are obtained when the phenylnitrile oxide isreplaced by an equivalent amount of other nitrile oxides in which thephenyl group is replaced by propyl,

amyl, octyl, tolyl, phenethyl, naphthyl, cyclohexyl, methylcycloheptyland cyclohexylmethyl respectively. In each case the softening point ofthe resultant resin is at least C. above that of the starting copolymer.

(0) When the procedure of (a) is repeated using an equivalent amount ofphenylene nitrile oxide, a crosslinked thermostat resin is obtained.

EXAMPLE VHI Post-treatment with aldehydes and ketones (a) Into a3-necked flask equipped with stirrer, reflux condenser, and athermometer there are placed 0.2 mole of a copolymer prepared as inExample I, 0.33 mole of paraformaldehyde and 75 parts of dry dioxane and0.25 part of NaOH. The reaction mixture is stirred and heated on a steambath for 12 hours and then subjected to vacuum distillation for removalof solvent and recovery of the product. Upon testing, the product isfound to still have its acetylenic linkage and to have added thereto arnethylol group.

(b) The procedure of the proceeding paragraph is repeated a number oftimes using individually in place of the paraformaldehyde an equivalentweight of acetaldehyde, benzaldehyde, beta-phenylacetaldehyde andbetacyclohexylacetaldehyde. In each case the postreacted product isfound to still have the acetylenic group intact and to have addedthereto secondary alcohol groups.

(c) The procedure of the above paragraph (a) is repeated a number oftimes using individually in place of the paraformaldehyde an equivalentweight of acetone, diphenylketone, diethylketone, methylethylketone anddicyclohexylketone. In each case the postreacted product is found tohave retained its acetylenic group and to have added thereto tertiaryalcohol groups.

EXAMPLE IX Postbromination of a polymeric acetylenic alcohol (a) Theprocedure of Example II is repeated except that in place of thecopolymer of Example I, there is used an equivalent amount of polymericacetylenic alcohol produced in Example VIII(a). The resulting copolymerhas repeating units represented by the Formula L and Formula N as givenabove. When the amount of bromine is not greatly in excess of 1 mole peracetylenic group therein, the postreacted polymer product has asubstantial number of repeating units of Formula L therein, as well asrepeating units of the starting copolymer. When a considerable excess ofbromine used is over the mole per mole ratio, there are also presentrepeating units of Formula M as well as the other repeating unitsindicated above, particularly when more than 2 moles of bromine are usedper acetylenic group.

EXAMPLE X (a) The acetylenic alcohols of Example VIII are made morewater soluble by reaction with one or more moles of ethylene oxide peracetylenic group using 15-20 psi. and 35 C. with an amount of LiOH inmethanol to give about 1% LiOH based on total weight of reagents.

(b) The procedure of paragraph (a) when repeated with propylene oxidegives similar results.

(0) When the procedure of above paragraph (a) is repeated using anequivalent amount of butane diepoxide, using tributylamine to catalyzethe reaction at room temperature, a crosslinked insoluble polymer isobtained.

EXAMPLE XI Postreacted to produce metallic derivatives (a) A copolymerproduced according to the procedure of Example I is dissolved ormaintained in suspension in liquid ammonia and a solution of sodamide inliquid ammonia is added thereto in sufficient proportion to provide aslight excess of one mole of sodamide per acetylenic group in thecopolymer. In place of the sodamide solution, the sodamide can be formedin situ by adding small pieces of metallic sodium to the liquid ammonia.The reaction is continued for a period of about 2 hours after thedesired amount of sodamide or sodium has been added. The polymericmetallic derivative is recovered by allowing the ammonia to evaporategradually and then the precipitate is dissolved in dioxane and theresulting solution is filtered. Tests on the polymeric product show thatthe sodium has replaced the hydrogen in the terminal acetylenic groups.

(b) The polymer metallic derivative is dissolved or suspended in dioxaneand reacted with dioxane solutions or suspensions of copper chloride,zinc chloride and cobalt chloride respectively to replace the sodium bythe respective other metals.

(c) An alkyl radical is added onto the acetylenic group in place of thesodium by adding an alkyl halide gradually to a dioxane solution of thesodium acetylene polymer. In this case the alkyl group replaces thesodium and sodium chloride is precipitated. The alkyl acetylenederivative polymer is subsequently recovered by dissolving in ether ordioxane and separated from the precipitated salt by filtration.

(d) Lithium is added to the acetylenic group by substituting butyllithium for the sodamide used above in paragraph (a).

EXAMPLE XII The procedure of Example I is repeated three times using thefollowing monomeric mixtures respectively:

(a) 75 parts styrene, 25 parts 3-butyn-l-yl acrylate.

(b) 50 parts styrene, 50 parts 3-butyn-l-yl acrylate.

(c) 90 parts styrene, parts 3-butyn-l-yl acrylate.

(d) Each of the three above products is postbrominated according to theprocedure of Example 11 to give brominated products having repeatingunits shown in the above Formulas A and B.

(e) Each of the three above products is decaboronated according to theprocedure of Example V and the decaboronated products have repeatingunits having the above Formulas C and D.

(f) Each of the three above products is crosslinked both thermally andalso with 10% styrene monomer according to the procedures of ExamplesIII and IV and the crosslinked copolymers have crosslinkages shown inFormulas E and F.

(g) Each of the three above products is post-treated with formaldehydeand diethylamine according to Example VI and the reaction products haverepeating units of Formula G.

(h) Each of the three above products is reacted with phenylnitrile oxideaccording to the procedure of Example VII(a) and the reaction productshave repeating units corresponding to above Formula H.

(i) Each of the three above products is reacted with formaldehydeaccording to the procedure of Example VIII(a) and the reaction productshave repeating units corresponding to above Formula K.

(j) The products prepared according to preceding paragraph (i) arebrominated according to the procedure of Example IX using 2.5 moles ofbromine per acetylenic In the (g) products:

I and C 0 O CHLCHZOEC CHzN(CzII5)z (Formula G) group present in thepolymer and the brominated prod ucts have repeating units therein of theabove Formulas L and M.

(k) Each of the acetylenic alcohol products from Paragraph (i) isreacted with ethylene oxide according to the procedure of Example X(a)and the reaction products have repeating units therein of the aboveFormula N.

(1) Each of the three above products from (a), (b) and (c) is suspendedor dissolved in liquid ammonia and reacted with sodamide according tothe procedure of Example XI(a) and the reaction products have repeatingunits therein of the formula shown below as Formula 0'. Portions ofthese products are further reacted with CuCl as in Example XI(b) andthese products have repeating units therein of the formula shown belowas Formula P.

(m) Each of the above procedures of paragraphs (a) through (I) isrepeated using the block copolymerization technique of Example Ia toproduce a center core of styrene in the linear chain and terminalportions of the acetylenic repeating units. In each of thepostreactions, similar repeating units are obtained as with the randomcopolymers used above but the postreacted repeating units are at the twoends of the block copolymers.

The repeating units in the various products produced in the aboveexample have the following structural formulas. In each product therepeating units from styrene are present. In the (a), (b) and (0)products the repeating units from 3-butyn-l-yl acrylate are alsopresent, and these repeating units are present in each of the subsequentreaction products to the extent that they remain unreacted.

From 3-butyn-1-yl-acrylate:

I -CH I0 I'I C C 0 00112011205011 The following repeating units are alsopresent in various products as indicated below:

In the (d) products:

From styrene:

-CH2 0 I'I- CH-C-GHa x COOCHgCHgC=CH (Formula F i COOCHgCHgCzCII(ILOOCH2CH2CICII CIIgClI- I (Formula E) In the (h) products:

CH2CH- (Formula H) 13 14 In the (i) products: In the (k) products:

-CH2CH- -CH2 CH- C O O CHZOHQCEC OHZOH and (E 0 01320132050 CHzO(CHzCHz) O H (Formula K) (Formula N) In the (j) products:

-CH2 CH- -CH2CH- COOCH2OH20=C=COH2OH and (EOOCHzGHzCBrzCBr-zOHzOH Br Br(Formula M) (Formula L) In the (1) products:

CH2OH- and GH2 OH OOCHzCHzCECNa COOCHzCHzCECCu (Formula 0') (Formula I?EXAMPLE XIII (e) 2-benzyl-3-butyn-l-yl methacrylate The procedure ofExample XII is repeated a number (f) 4'Pemyne'2'y1 acrylate of timesincluding the various postreactions except that g methacrylate in thepreparation of the starting copolymers methyl p'e yny phenyl acrylatemethacrylate is used instead of the styrene. Similar results ipethynylbenzyl methacrylate are obtained in each case, except that inthe polymer (3) Lethynylcyclohexyl acrylate structures, the repeatingunit for methyl methacrylate is In each case similar products areobtained as in Example present instead of the repeating unit forstyrene. This XII, and the various copolymers have in addition to therepeating umt has the structure repeating units derived from styrene.the following re- CH2C(GH3) peating units respectively:

000cm (a) CH2CH The repeating units for the 3-butyn-1-yl acrylate arethe W QOEOH same as obtained in Example XII and the repeating units forthe various postreaction products of these repeating o H units are thesame as obtained in the correspondlng post- 0 0C (OH3)C OH reactions forExample XII. (c)

EXAMPLE XIV COOCHCHzCECH The procedure of Example XII is repeated anumber of times using individually in place of the styrene the followingcomonomers respectively: vinyl naphthalene, vinyl (d) CH2CH toluene,p-chlorostyrene, ethyl acrylate, vinyl chloride, COOCHCHZCEOHacrylonitrile, vinylidene chloride, vinyl acetate, vinyl ben- J3EEzoate, a-methyl styrene, isopropenyl propionate, methacrylonitrile andcyclohexyl acrylate. In each case similar (e) TOHEOWHS) results areobtained as in Example XII except that the COOCH2CHCECH correspondingrepeating units of the respective comono- CHZCGHa mers employed in thisexample are substituted for the repeating units for the styrene used inExample XII. The (t) OH2OH repeating units for the the acetylenicmonomer and for a) HzOEOH the various postreacted repeating units aresimilar to (g) CH1o 0H, those described in Example XII. C O O CHwHg)GH2O CH EXAMPLE XV oniomo ns The procedure of Example XII is repeated anumber (m of times using the corresponding methacrylate in place of the3-butyn-1-yl acrylate. Similar results are obtained as 00006114050}! inExample XII except that in the various copolymers, (i) CH2O(OH3)' therepeating units of the acetylenic methacrylate have the followingrepeating unit structure:

The various postreacted products have repeating unit structures similarto those described in Example XII except that in the upper portion ofeach of the repeating In the various postreacted products of thisexample, the repeating units derived from the acetylenic units havevarious groups attached thereto in a manner similar to the attachment ofvarious reagent groups as illustrated in g j' Structure 15 CH2C(CH3)Instead of Example XII, but in these cases by addition to the zacetylenic groups in the respective acetylenic monomers EXAMPLE XVI usedin this example.

When x is used in some of the above formulas, this i proclaim? f l XII1s repeated a number indicates an integer having a value of 1 or more.Where of times using rndrvrdually in place of the 3-butyn-1-yl n is used1s indicates a plurallty of groups, that 1s at acrylate, the followingacetylemc monomers. least 2 and preferably at least 4 (a) 3-butyn-2-ylacrylate The copolymers of this invention advantageously have (b)3-butyn-2-yl methacrylate a molecular weight of at least 500 andpreferably at least (0) l-phenyl-3-butyn-l-yl acrylate 5000. There is noupper limit since this is generally deter- (d) 1-cyclohexyl-3-butyn-1-ylacrylate mined by practical considerations. However, there is generallyno particular advantage in exceeding molecular weights of about 800,000.

Preferred comonomers for use in preparing the copolymers of thisinvention are the vinyl and vinylidene comonomers represented by theformula:

OH2=C'R' it and the repeating units derived from such comonomers arerepresented by the formula -CH2C(R) In these formulas, R representshydrogen or the methyl or cyano radical, preferably hydrogen or methyl;Y represents:

(a) Hydrocarbon, including alkyl, aryl, alkaryl, aralkyl, cycloalkyl,alkylcycloalkyl, cycloalkyl-alkyl;

(b) Cyano; and

(c) COOR" wherein R" is as defined above.

The hydrocarbon groups of R and R preferably have 1-8 carbon atoms.Typical repeating units for such comonomers are those of methylacrylate, acrylonitrile and vinyl toluene which have the followingstructures respectively.

CHzCH; -CH2CH;

000C113 CN mports Typical examples of the comonomers of the aboveformula that can be used in preparing the copolymers of this inventioninclude the following: styrene, a-methyl styrene, vinyl toluene, vinylxylene, isopropenyl toluene, vinyl naphthalene, isopropenyl naphthalene,vinyl diphenyl, isopropenyldiphenyl, ethylene, propylene, butene- 1,Z-methyI-butene-l, hexene-l, Z-methyl-hexene-l, decene- 1,3-phenylpropene-l, 4-phenylbutene-1, 2-methy1-3- phenylbutene-l, vinylcyclohexane, vinyl cycloheptane, vinyl methylcyclohexane, vinylmethylcycloheptane, 3- cyclohexyl-butene-l,2-methyl-3-cycloheptyl-butene-l, 4- cyclopentyl-pentene-l,acrylonitrile, methacrylonitrile, vinylidene cyanide, methyla-cyanoacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate,propyl methacrylate, phenyl acrylate, phenyl methacrylate, benzylacrylate, naphthyl acrylate, cyclohexyl acrylate, cyclohexylmethacrylate, etc.

Typical hydrocarbon monovalent radicals as represented by R, R" and Rinclude: methyl ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl,phenyl, tolyl, xylyl, naphthyl, metylnaphthyl, ethylnaphthyl. diphenyl,methyldiphenyl, benzyl, phenethyl, phenylpropyl, cyclohexyl,

cyclohexylmethyl, cycloheptyl, methylcycloheptyl. While the hydrocarbongroups listed above do not contain ethylenic unsaturation, groupscontaining unsaturation can be used provided that the unsaturation doesnot cause premature crosslinking of the linear copolymers. However,there is no particular advantage in their use. Generally, it ispreferable to use alkyl, aryl, aralkyl, alkaryl, cycloalkyl,alkylcycloalkyl and cycloalkyl-alkyl groups.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention and it is not intended to limit the invention tothe exact details shown above except insofar as they are defined in thefollowing claims.

The invention claimed is:

1. A linear polymeric composition having an average polymeric molecularweight of at least 5,000 and having a plurality of acetylenic repeatingunits in the polymeric molecules in which the repeating units of thelinear polymeric molecules comprise 1-85 acetylenic repeating units per100 repeating units in the polymeric molecules, said acetylenicrepeating units having the formula:

16 wherein R represents hydrogen or methyl, Z is a divalent hydrocarbonradical of 2-10 carbon atoms, and the remainder of said linear polymericmolecules consisting essentially of repeating units derived from apolymerizable comonomer selected from the class consisting of vinyl andvinylidene comonomers.

2. A polymer of claim 1 in which the remainder of said polymericmolecules consists essentially of repeating units having the formula:

3. A polymer of claim 1 in which the remainder of said polymericmolecules consists essentially of repeating units having the formula:

4. A polymer of claim 1 in which the remainder of said polymericmolecules consists essentially of repeating units having the formula:

CHQC(CH3) C 0 0 CH3 5. A polymer of claim 1 in which the remainder ofsaid polymeric molecule consists essentially of repeating units havingthe formula:

CHzCH- 6. A polymer of claim 1 in which the remainder of said polymericmolecule consists essentially of repeating units having the formula:

7. A postbrominated polymer of claim 1 in which said polymer molecule inaddition to the repeating units recited in claim 1 also contain at leastone repeating unit selected from the class of consisting of:

8. A polymer of claim 1 postreacted with formaldehyde and an amine ofthe formula R' NH, wherein R is hydrogen or a hydrocarbon radical of 18carbon atoms, and having in addition to the polymeric repeating unitsrecited in claim 1 a plurality of repeating units:

9. A polymer of claim 1 postreacted with a nitrile oxide having theformula RCNO wherein R is a hydrocarbon radical of 1-8 carbon atoms andhaving in addition to the polymericrepeating units recited in claim 1 aplurality of repeating units:

O\N/ O 10. A polymer of claim 1 postreacted with R' CO wherein R ishydrogen or a hydrocarbon radical of 1-8 carbon atoms and having inaddition to the polymeric repeating units recited in claim 1 a pluralityof repeating units:

11. A postbrominated polymer of claim 1 in which said polymer moleculein addition to the repeating units 17 recited in claim 1 also contain atleast one repeating unit selected from the class consisting of:

13. A polymer of claim 1 postreacted with a nitrile oxide having theformula R"CNO, wherein R" is a hydrocarbon radical of 1-8 carbon atoms,and having in addition to the polymeric repeating units recited in claim1 a plurality of repeating units:

References Cited UNITED STATES PATENTS 3,183,216 5/1965 Cohen et a126089.5 3,254,115 5/1966 Cohen et a1. 260486 3,293,226 12/1966 deSchrijver 26096HAL 3,437,688 4/1969 Schwartz 260486 OTHER REFERENCESRoberts: Basic Principles of Organic Chemistry, published by W. A.Benjamin, 1110., New York, NY. (1964), pp. 216.

HARRY WONG, 111., Primary Examiner U.S. Cl. X.R.

